KR20180003352A - Transparent conductor and display apparatus comprising the same - Google Patents

Abstract

A transparent conductor and a display device including the same are provided. The transparent conductor includes a base layer and a transparent conductive layer formed on a base layer. The transparent conductive layer includes a metal nanowire and a matrix impregnated with the metal nanowire. The matrix is formed of a composition for a matrix comprising inorganic hollow particles, fluorine-containing monomer or oligomer thereof, photosensitive resin, crosslinking agent and initiator. The productivity of the transparent conductor can be improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent conductor and a display device including the transparent conductor.

The present invention relates to a transparent conductor and a display device including the transparent conductor.

The metal nanowire-containing transparent conductor may be included in a touch screen panel or the like of a display device. The metal nanowire-containing transparent conductor has a structure in which a conductive network formed of metal nanowires is impregnated in the matrix.

The metal nanowire-containing transparent conductor can be used for a display device such as a touch panel by patterning. A pattern can be directly formed on the transparent conductive layer by laser irradiation. Alternatively, wet etching may be performed by photolithography. The wet etching includes a step of forming a photoresist on a transparent conductive layer, and then developing and developing the UV. As the photoresist, a liquid photoresist or a film type photoresist can be used. Film-type photoresists are expensive, but they can be etched with a roll-to-roll process, resulting in high productivity. However, there are problems such as the adhesion of the transparent conductive layer and the film type photoresist, adhesion after the development, and adhesion depending on the composition of the etching solution. There is a method of coating a liquid photoresist on a transparent conductive layer and developing it, but there is a problem that productivity is significantly lowered compared with a roll-to-roll process.

The background art of the present invention is described in Korean Patent Publication No. 2012-0053724.

A problem to be solved by the present invention is to provide a transparent conductor excellent in productivity and excellent in pattern forming ability because it can be patterned without using a separate photoresist.

Another object to be solved by the present invention is to provide a transparent conductor which is capable of forming a pattern by developing and cleaning without performing etching and cleaning.

Another object to be solved by the present invention is to provide a transparent conductor comprising a transparent conductive layer which is excellent in adhesion to a substrate layer and is not affected by development and / or cleaning during patterning, .

Another object of the present invention is to provide a transparent conductor having excellent optical transparency and low sheet resistance.

The transparent conductor of the present invention comprises a base layer and a transparent conductive layer formed on the base layer, wherein the transparent conductive layer comprises a metal nanowire and a matrix impregnated with the metal nanowire, , A fluorine-containing monomer or oligomer thereof, a photosensitive resin, a crosslinking agent and an initiator.

The display device of the present invention may include the transparent conductor of the present invention.

The present invention provides a transparent conductor of high sensitivity which is excellent in productivity and excellent in pattern forming ability because it can be patterned without using a separate photoresist.

The present invention provides a transparent conductor which is capable of forming a pattern by developing and cleaning without etching and cleaning.

The present invention provides a transparent conductor comprising a transparent conductive layer which is excellent in adhesion to a base layer and is not affected by development or cleaning during patterning and thus is not peeled off from the base layer.

The present invention provides a transparent conductor having excellent optical transparency and low sheet resistance.

1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention.
2 is a schematic diagram of a patterning process of a transparent conductor according to an embodiment of the present invention.
3 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.
4 is a cross-sectional view of a display device according to an embodiment of the present invention.
5 is a cross-sectional view of a display device according to another embodiment of the present invention.

The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

The terms "upper" and "lower" in this specification are defined with reference to the drawings, wherein "upper" may be changed to "lower", "lower" What is referred to as "on" may include not only superposition, but also intervening other structures in the middle. On the other hand, what is referred to as "directly on," " directly above, "or" directly formed, "

As used herein, "(meth) acrylic" means acrylic and / or methacrylic.

As used herein, "aspect ratio" means the ratio (L / d) of the longest length (L) of the metal nanowire to the shortest diameter (d) of the cross section of the metal nanowire.

Hereinafter, a transparent conductor according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention. 2 is a schematic view illustrating a patterning process of a transparent conductor according to an embodiment of the present invention.

Referring to FIG. 1, a transparent conductor 100 according to an exemplary embodiment of the present invention may include a base layer 110 and a transparent conductive layer 120.

The base layer 110 may support the transparent conductive layer 120 and protect the transparent conductive layer 120. The base layer 110 may include a resin film having a light transmittance of 85% to 100%, more specifically 90% to 99% at a wavelength of 550 nm. Within this range, the optical characteristics of the transparent conductor can be improved. Specifically, the resin may be selected from the group consisting of polyester, polyolefin, polysulfone, polyimide, silicone, polystyrene, polyacrylic, polyvinyl chloride resin including polycarbonate, cyclic olefin polymer, polyethylene terephthalate and polyethylene naphthalate But is not limited thereto. The base layer 110 may have a thickness of 10 占 퐉 to 200 占 퐉, specifically 30 占 퐉 to 150 占 퐉, more specifically, 30 占 퐉 to 100 占 퐉. Within this range, the substrate layer may be used for the transparent conductor. 1, the base layer 110 is a single layer, but the base layer may be a multi-layer, and a functional layer may be formed on the base layer 110 although not shown in FIG. The functional layer may be formed as a separate layer independently of the substrate layer or may be formed such that one side of the substrate layer is a functional layer, providing hard coating, corrosion prevention, antireflection, adhesion enhancement, oligomer elution preventing function and the like .

The transparent conductive layer 120 is formed on the substrate layer 110 and can provide conductivity and flexibility to the transparent conductive material 100. [ The transparent conductive layer 120 may be formed directly on the base layer 110.

The transparent conductive layer 120 may include a matrix 122 in which the metal nanowires 121 and the metal nanowires 121 are impregnated. FIG. 1 illustrates a case where the metal nanowires are completely impregnated into the transparent conductive layer 120, but the present invention is not limited thereto. The metal nanowires may be partially exposed to the outside of the transparent conductive layer 120. As shown in FIG. 1, when the metal nanowires 121 are completely impregnated into the transparent conductive layer 120, the oxidation of the metal nanowires can be reduced and the sheet resistance of the transparent conductive material 100 can be further lowered.

The metal nanowires 121 can provide conductivity to the transparent conductor by forming a conductive network. Since the metal nanowires 121 have a nanowire shape, it is possible to provide the transparent conductor with flexibility and flexibility. The metal nanowires 121 may have an aspect ratio of 10 to 5,000. Within this range, a high conductivity network can be realized even at a low metal nanowire density, and the sheet resistance of the transparent conductor can be lowered. Specifically, the metal nanowire may have an aspect ratio of 500 to 1,000, more specifically 500 to 700. The metal nanowire may have a cross-sectional diameter of more than 0 nm but not more than 100 nm, specifically, 10 nm to 100 nm, more specifically, 10 nm to 30 nm. Within this range, a high aspect ratio can be achieved to increase the conductivity of the transparent conductor and lower the sheet resistance. The metal nanowires may have a maximum length of 10 탆 or more, specifically 10 탆 to 50 탆. Within this range, a high aspect ratio can be achieved to increase the conductivity of the transparent conductor and lower the sheet resistance. The metal nanowire may be formed of a metal including at least one of silver, copper, aluminum, nickel, and gold. The metal nanowires 121 may be included in the transparent conductive layer 120 in an amount of 40 wt% to 80 wt%, specifically 50 wt% to 70 wt%. Within the above range, the conductivity of the transparent conductor can be increased.

The matrix 122 may be formed on the base layer 110 to strengthen the bond between the base layer 110 and the metal nanowires 121. The matrix 122 impregnates the conductive network of the metal nanowires 121 to prevent oxidation of the metal nanowires, thereby preventing the sheet resistance of the transparent conductor from rising. Further, the matrix 122 can improve the optical characteristics, chemical resistance, solvent resistance, durability (reliability), etchability, etc. of the transparent conductor.

The matrix 122 may be a single layer formed of a composition for a matrix comprising inorganic hollow particles, a fluorine-containing monomer or oligomer thereof, a photosensitive resin, a crosslinking agent, and an initiator. The transparent conductor 100 according to the present embodiment can be patterned without using a separate photoresist, so that productivity can be excellent.

2 schematically shows a patterning process of the transparent conductor 100 according to the present embodiment. Referring to FIG. 2, a mask pattern having a desired pattern is disposed on the transparent conductor 100 according to the present embodiment, and UV can be irradiated. The amount of UV irradiation can be changed depending on the thickness of the matrix, the material of the matrix, and the like. UV irradiation can form a UV-exposed portion (A) and a UV-unexposed portion (B) in the matrix. After removing the mask pattern, the transparent conductor is developed and cleaned to remove the matrix of the UV unexposed portions. After the etching solution treatment and the cleaning, post curing and hard baking are performed, a transparent conductor having a desired pattern can be produced. The etchant may be a mixture of nitric acid, acetic acid, and phosphoric acid, but is not limited thereto. When the transparent conductor 100 is patterned by addition of an etching solution treatment, pattern formation can be performed well even when the concentration of the etchant is diluted compared to the conventional method. However, the pattern formation may be completed by developing and cleaning without etching and cleaning. Further, since the transparent conductive layer 120 is excellent in adhesion to the base layer 110, the transparent conductive layer 120 is not affected by development, cleaning, or the like during patterning, and may not be peeled off from the base layer.

Hereinafter, the composition for a matrix will be described in detail.

The inorganic hollow particles and the fluorine-containing monomer or oligomer thereof can improve the optical characteristics of the transparent conductive layer, reduce the haze of the transparent conductive material, and increase the light transmittance. Specifically, the transparent conductor 100 may have a haze of 1.5% or less, specifically 0% to 1.5% at a wavelength of 550 nm. The transparent conductor 100 may have a total light transmittance of 90% or more, specifically 90% to 99% in a visible light region, for example, a wavelength of 400 nm to 700 nm. Within this range, transparency is good and can be used as a transparent conductor. At the same time, the inorganic hollow particles and the fluorine-containing monomer or oligomer thereof affect pattern-forming properties of the transparent conductive layer together with the following photosensitive resin, thereby improving the pattern forming ability of the transparent conductive layer and increasing the adhesion to the substrate layer The transparent conductive layer can be prevented from being peeled off from the substrate layer even by development or cleaning.

The inorganic hollow particles may have a refractive index of 1.4 or less, specifically 1.33 to 1.38. The average particle size (D50) of the inorganic hollow particles may be 30 nm to 100 nm, specifically 40 nm to 70 nm. May be included in the matrix within the above range, and may be advantageously applied as a transparent conductive layer. The inorganic hollow particles may be selected from the group consisting of silica, mullite, alumina, silicon carbide (SiC), MgO-Al ₂ O ₃ -SiO ₂ , Al ₂ O ₃ -SiO ₂ , MgO-Al ₂ O ₃ -SiO ₂ -LiO ₂ , Or a mixture thereof, and they may be surface-treated. The fluorine-containing monomer or oligomer thereof may comprise a fluorine-containing (meth) acrylic monomer or oligomer thereof. Fluorine-containing monomers can be used in LINC series (eg LINC-3A) from Kyoeisha and OPTOOL series (eg AR-100) from DAIKIN.

The inorganic hollow particles and the fluorine-containing monomer or oligomer thereof may each be contained by itself, or may be contained as a solution containing both of them. The solution may further contain an initiator, a (meth) acrylic monomer, and a solvent such as methyl isobutyl ketone. The solution containing the inorganic hollow particles and the fluorine-containing monomer or oligomer thereof as a whole, or a solution containing the inorganic hollow particles and the fluorine-containing monomer or oligomer as a whole may have a refractive index of 1.42 or less, specifically 1.33 to 1.38. Within the above range, the optical characteristics of the transparent conductive layer may be good. The solution may include, but is not limited to, commercially available products such as A-2505 (Pelnox), OPSTAR TU series (JSR), and the like.

The inorganic hollow particles and the fluorine-containing monomer or oligomers thereof may be contained in an amount of 10% by weight to 50% by weight, specifically 20% by weight to 40% by weight or 30% by weight to 50% by weight, based on the solid content in the composition for a matrix. Within this range, the transparency of the film may be improved to increase the transmittance and improve the adhesion of the matrix to the substrate layer. As used herein, "solids" means the entirety of the composition for a matrix except for the solvent.

The photosensitive resin is cured to form a matrix, and the transparent conductor can be patterned by UV exposure. The photosensitive resin may include a positive or negative photosensitive resin upon UV irradiation.

The photosensitive resin may have a weight average molecular weight of 5000 to 10000, specifically 5500 to 9000. Within this range, there may be an effect that the pattern formation is good and the adhesion of the matrix is improved. The photosensitive resin is a general-purpose photosensitive resin for a photoresist, and is preferably a photosensitive resin for a photoresist, such as phenol novolac resin, cresol novolak resin, naphthol novolac resin, novolak resin using various phenolic compounds, Resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthol Resins, aminotriazine-modified phenol resins, and the like. Of these, novolac resins may be preferable in view of excellent patterning property when they are mixed together with inorganic hollow particles and fluorine-containing monomers or oligomers thereof.

The photosensitive resin may be contained in the matrix composition in an amount of 30% by weight to 65% by weight, specifically 40% by weight to 60% by weight, based on the solids content. Within the above-mentioned range, there is an effect that the pattern is well formed by exposure, development, cleaning, etc., and the adhesion and coating properties of the matrix are excellent, and the conductivity of the metal nanowires is not affected.

The crosslinking agent can cure the photosensitive resin, the fluorine-containing monomer or oligomer thereof. The crosslinking agent may be a compound containing a double bond such as a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resol resin, an epoxy compound, an isocyanate compound, an azide compound or an alkenyl ether group, An anhydride-based compound, an oxazoline-based compound, and the like. Among them, when the melamine compound is mixed with the inorganic hollow particles and the solution containing the fluorine-containing monomer or oligomer, the curing rate of the composition for a matrix is increased and the formation of a pattern of the transparent conductor can be facilitated.

Examples of the melamine compound include compounds obtained by methoxymethylating one to six methylol groups of hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, 1 to 6 of the methylol groups of hexamethylol melamine may be acyloxymethylated and the like. The guanamine-based compound is a compound obtained by methoxymethylating one to four methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine and tetramethylolguanamine, Tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, and the like. The glycoluril compound may be 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6- Tetrakis (hydroxymethyl) glycoluril and the like. The urea compound may be at least one selected from the group consisting of 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea And the like. Examples of the resol resin include phenol, alkylphenol such as cresol and xylenol, phenol such as phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A or bisphenol F, naphthol, dihydroxynaphthalene, And polymers obtained by reacting an aldehyde compound under an alkaline catalyst condition. Examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide. The compound containing a double bond such as the alkenyl ether group may be any one of ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol di Vinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetra Vinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like. The acid anhydride compound may be selected from the group consisting of phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4' Propylidene) diphthalic anhydride, and 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride; Alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, anhydrous methylene tetrahydrophthalic anhydride dodecenylsuccinic anhydride and anhydrous trialkyltetrahydrophthalic acid, and the like can be given .

The crosslinking agent may be contained in the matrix composition in an amount of 1% by weight to 10% by weight, specifically 1% by weight to 5% by weight, based on the solids content. Within the above range, the process margin of the pattern formation can be controlled by controlling the degree of crosslinking of the photosensitive resin, and pattern formation can be facilitated.

The initiator may cure the photosensitive resin, the fluorine-containing monomer or oligomer thereof, and may include conventional initiators known to those skilled in the art. For example, the initiator may include a photoinitiator such as an initiator that generates an active radical, an initiator that initiates cationic polymerization, and the like. The initiator may be an acylphosphine compound such as a halogenated hydrocarbon derivative (for example, a derivative having a triazine skeleton or a derivative having an oxadiazole skeleton), acylphosphine oxide, an oxime compound such as hexaarylbimidazole or oxime derivative , Organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenones, hydroxyacetophenones, and the like. Among them, the oxime derivatives are preferable because they can easily form a pattern at a low exposure dose. Oxime derivatives can be prepared by reacting 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3- cyclopentylpropanone- 2-one, 3-acetoxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino- 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino- Propan-1-one, and the like.

The initiator may be contained in the matrix composition in an amount of 1 to 15% by weight, specifically 1 to 10% by weight, based on the solids content. Within this range, it may be effective to facilitate pattern formation even at a low exposure dose and to improve the adhesion of the matrix layer in the post-curing process.

The composition for a matrix may further include at least one of an adhesion promoter and an antioxidant.

The adhesion promoter improves the adhesion of the transparent conductive layer to the base layer, thereby reducing the thickness of the transparent conductive layer and enhancing the reliability of the transparent conductive layer. The adhesion promoter may include at least one of a silane coupling agent, a monofunctional (meth) acrylic monomer, and a bifunctional (meth) acrylic monomer. These may be included singly or in combination of two or more. The silane coupling agent is a commonly known silane coupling agent and includes 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- A silane coupling agent having an epoxy group such as oxypropyltrimethoxysilane; A silane coupling agent containing a polymerizable unsaturated group such as vinyltrimethoxysilane; Amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; And 3-chloropropyltrimethoxysilane can be used. The monofunctional or bifunctional (meth) acrylic monomer is a monofunctional or bifunctional (meth) acrylic monomer of C3 to C20 polyalcohol, such as isobornyl (meth) acrylate, cyclopentyl (meth) (Meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di Di (meth) acrylate, and the like. The adhesion promoting agent may be included in the composition for the solid matrix-based matrix in an amount of 5% by weight to 20% by weight, specifically 5% by weight to 15% by weight. Within the above range, the reliability and conductivity of the transparent conductor can be improved, and the adhesion of the transparent conductive layer can be improved.

Antioxidants can prevent oxidation of the network of metal nanowires. The antioxidant may include one or more of triazole-based, triazine-based, phosphite-based phosphorus, Hindered amine light stabilizer (HALS) based, phenol based, and metal acetylacetonate based antioxidant. These may be included singly or in combination of two or more. Specifically, the phosphorus antioxidant is tris (2,4-di-tert-butylphenyl) phosphite and the phenol antioxidant is pentaerythritol tetrakis (3- (3,5- Roxy phenyl) propionate). The antioxidant for HALS is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4- piperidinyl) sebacate, bis (2,2,6,6-tetramethyl-5-piperidinyl) sebacate, dimethyl succinate having 4-hydroxy-2,2,6,6-tetramethyl-1-piperidin- N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- Ethylamine) -1,3,5-triazine, and the like. The metal acetylacetonate antioxidant may include, but is not limited to, tris (acetylacetonato) iron (III), tris (acetylacetonato) chromium (III), and the like. The antioxidant may be contained in the composition for solid matrix-based matrices in an amount of 0.01 wt% to 10 wt%, specifically 0.5 wt% to 7 wt%. In this range, oxidation of the metal nanowires is prevented, pattern uniformity of the patterned transparent conductor is high, and it is advantageous for realizing a fine pattern.

The composition for a matrix may further comprise a solvent. The solvent may include at least one of ketone solvents such as propylene glycol monomethyl ether acetate (PGEMA) and methyl isobutyl ketone, and alcohol solvents such as isopropyl alcohol and ethanol.

The composition for a matrix may further comprise an additive. The additive may include a surfactant such as a fluorine-based surfactant, an antistatic agent, an ultraviolet absorber, a viscosity modifier, a heat stabilizer, a dispersant, a thickener, and the like.

The composition for a matrix may have a viscosity of 0.1 cP to 20 cP at 25 캜. Within the above range, the coating property of the matrix composition is improved and uniformly coated with a thin film, so that the transparent conductive layer can have uniform physical and chemical properties.

The transparent conductive layer 120 may have a thickness of 1 占 퐉 or more and 2 占 퐉 or less, specifically, 1 占 퐉 or more and 1.7 占 퐉 or less. Within this range, it can be used in an optical display device, has good pattern forming ability, good adhesion to a base layer, and excellent optical properties.

The transparent conductor 100 may have a sheet resistance of 100 Ω / □ or less, specifically 50 Ω / □ or less, more specifically 30 Ω / □ to 50 Ω / □, as measured by a 4-probe or a non-contact sheet resistance meter. In the above range, since the sheet resistance is low, it can be used as an electrode film for a touch panel, and can be applied to a large-area touch panel. The thickness of the transparent conductor 100 may be 10 占 퐉 to 250 占 퐉, specifically, 50 占 퐉 to 200 占 퐉. In the above range, it can be used as a transparent electrode film including a film for a touch panel, and can be used as a transparent electrode film for a flexible touch panel. The transparent conductor 100 is in the form of a film and is patterned by etching or the like, and can be used as a transparent electrode film of a touch panel, an E-paper, or a solar cell.

Hereinafter, a transparent conductor according to another embodiment of the present invention will be described with reference to FIG. 3 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.

Referring to FIG. 3, the transparent conductor 100 'of the present embodiment includes a transparent conductive layer 120' and a transparent conductive layer 120a, which are patterned into a transparent conductive layer 120a and an empty space 120b. Is substantially the same as the transparent conductor 100 of the embodiment. The transparent conductive layer 120 'may be formed by patterning the transparent conductive layer 120 according to an embodiment of the present invention. Specifically, the patterning is the same as that described above with reference to FIG. Further, in order to prevent the metal nanowires of the patterned layer that has been hardened from being etched from being etched during etching, it is possible to use the etching solution at a low concentration or shorten the etching time.

Hereinafter, an optical display device according to an embodiment of the present invention will be described with reference to FIG. 4 is a cross-sectional view of an optical display device according to an embodiment of the present invention.

4, an optical display device 200 according to an embodiment of the present invention includes a display unit 210, a polarizer 220, a transparent electrode member 230, a window film 240, an adhesive layer 250, And the transparent electrode member 230 may be formed of a transparent conductor according to embodiments of the present invention. 4 illustrates a structure in which the display unit 210, the polarizer 220, the transparent electrode member 230, and the window film 240 are stacked in this order. The display unit 210, the transparent electrode member 230, The polarizer 220, and the window film 240 may be stacked in this order.

The display unit 210 is for driving the optical display device 200 and may include an optical element including an OLED, an LED, or an LCD device formed on a substrate and a substrate. In one embodiment, the display portion 210 may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protective layer, and an insulating layer. In other embodiments, the display portion 210 may include an upper substrate, a lower substrate, a liquid crystal layer positioned between the upper substrate and the lower substrate, and a color filter formed on at least one of the upper substrate and the lower substrate. 4 illustrates a structure in which the display unit 210 and the transparent electrode unit 230 are separately layered, but the transparent electrode unit 230 may be formed inside the display unit.

The polarizing plate 220 is formed on the display unit 210 to realize polarized light or to prevent reflection of external light to realize a display or improve a contrast ratio of the display. The polarizer 220 may be a polarizer alone. Alternatively, the polarizer 220 may include a polarizer and a protective film formed on one or both sides of the polarizer. Although not shown in FIG. 4, a polarizing plate may be further formed under the display unit 210 to improve the contrast ratio of the display. At this time, the polarizing plate may be formed on the display unit 210 by an adhesive layer.

The transparent electrode member 230 is formed on the polarizing plate 220 and can generate an electrical signal by detecting a change in capacitance generated when the transparent electrode member 230 is touched by contact or the like. The transparent electrode assembly 230 includes a base layer 110, a first electrode 231 and a second electrode 232 formed on one surface of the base layer 110, a third electrode (not shown) formed on the other surface of the base layer 110 233, and a fourth electrode 234. 4 shows a structure in which the third electrode 233 and the fourth electrode 234 / the substrate layer 110 / the first electrode 231 and the second electrode 232 are stacked in this order. However, the substrate layer 110 The third electrode 233 and the fourth electrode 234 / the base layer 110 / the first electrode 231 and the second electrode 232 may be stacked in this order.

The window film 240 may be formed at the outermost portion of the optical display device 200 to protect the optical display device 200. The window film 240 may be formed of a glass substrate or a flexible plastic substrate.

The adhesive layer 250 is formed between the display unit 210 and the polarizer 220, between the polarizer 220 and the transparent electrode unit 230, between the transparent electrode unit 230 and the window film 240, The polarizer 220, the transparent electrode 230, and the window film 240 can be strengthened. The adhesive layer 250 may be formed of a conventional optically transparent adhesive.

Hereinafter, an optical display device according to another embodiment of the present invention will be described with reference to FIG. 5 is a cross-sectional view of an optical display device according to another embodiment of the present invention.

5, an optical display device 300 according to another embodiment of the present invention includes a transparent electrode member 230 ', a third electrode 233 formed on one surface of the substrate layer 110, Except that the first electrode 231 and the second electrode 232 are further formed on the window film 240 'and the fourth electrode 234 and the fourth electrode 234, 200). ≪ / RTI >

Hereinafter, a method of manufacturing a transparent conductor according to an embodiment of the present invention will be described.

A method of manufacturing a transparent conductor according to an exemplary embodiment of the present invention includes coating a metal nanowire dispersion on a base layer to form a metal nanowire dispersion layer, coating the matrix composition on the metal nanowire dispersion layer, And curing the metal nanowire dispersion layer and the composition for a matrix.

The metal nanowire dispersion may contain metal nanowires. The metal nanowire dispersion may further include a solvent to further enhance the coating properties of the metal nanowire. The solvent may include, but is not limited to, water, an organic solvent such as alcohol, and the like. The metal nanowire dispersion may further contain a binder, an initiator, an additive, and the like. The additives may be dispersants, thickeners, and the like. The binder may include at least one of a (meth) acrylate-based monofunctional monomer and a (meth) acrylate-based polyfunctional monomer. The dispersing agent can increase the dispersion of the metal nanowires and the binder. Thickening agents can increase the viscosity of the metal nanowire dispersion. The binder, initiator, and additives may be included in the metal nanowire dispersion in an amount of 0.1 wt% to 50 wt%, specifically 5 wt% to 45 wt% based on solids. Within the above range, improvement of optical characteristics, prevention of increase in contact resistance, durability and chemical resistance of the transparent conductor can be improved. The metal nanowire dispersion can be prepared by mixing the metal nanowire-containing solution, for example, a commercially available product of Cambrios (e.g., ClearOhm Ink) with the solvent.

The composition for a matrix may be formed of a composition for a matrix containing inorganic hollow particles, a fluorine-containing monomer or oligomer thereof, a photosensitive resin, a crosslinking agent and an initiator.

The metal nanowire dispersion is then coated on the substrate layer to form a metal nanowire dispersion layer, the composition for the matrix is coated on the metal nanowire dispersion layer, and the metal nanowire dispersion layer and the matrix composition are cured A transparent conductive layer can be formed. The coating can be performed by, but not limited to, bar coating, slot die coating, gravure coating, and roll-to-roll coating. The coating thickness may be 1 탆 or more and 2 탆 or less, specifically, 1 탆 or more and 1.7 탆 or less. The curing can form a transparent conductive layer and increase the strength of the transparent conductive layer. The curing may include one or more of thermosetting, light curing. The thermal curing may be carried out at 40 캜 to 180 캜 for 1 minute to 48 hours. Photocuring can be carried out with a UV dose of 50 mJ / cm ² to 1,000 mJ / cm ² . The coating film for a transparent conductive layer can be dried before curing the coating film for a transparent conductive layer to shorten the curing time. Drying may be carried out at 40 캜 to 180 캜 for 1 minute to 48 hours.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example  One

45 parts by weight of silver nanowire-containing solution (Clearohm ink, 2% by weight of solid matter such as silver nanowires, etc.) was added to 55 parts by weight of distilled water of ultra pure water and stirred to prepare a silver nanowire dispersion.

37 parts by weight of a solution containing hollow silica and a fluorine-containing monomer (Pelnox Co., A-2505, hollow silica, including fluorine-containing monomer and initiator, refractive index: 1.33), a novolak resin-containing solution (Showa Denko, RY-25 ), 13 parts by weight of a hexamethoxymethylmelamine-containing solution as a crosslinking agent, 34 parts by weight of a solution containing an oxime ester-based initiator PBG304 (DKSH, 1- [9-ethyl-6- (2-methylbenzoyl) 3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime), and the solvent propylene glycol monomethyl ether acetate was added thereto to prepare a composition for a matrix having a solid concentration of 1.6 wt% . The composition for the matrix contained 37 wt% of the total of the hollow silica and the fluorine-containing monomer, 52 wt% of the novolac resin, 3 wt% of hexamethoxymethylmelamine, and 8 wt% of the oxime ester initiator based on the solid content.

The prepared silver nanowire dispersion was coated on a substrate layer (polycarbonate film, Teijin, thickness: 50 mu m) by a spin coater, dried in an oven at 140 DEG C for 90 seconds, and then coated with a bar coater Thereafter, the resultant was dried in an oven at 80 캜 for 120 seconds to form a transparent conductive layer having a thickness of 1.2 탆, thereby preparing a transparent conductor.

Example  2

A transparent conductor was prepared in the same manner as in Example 1, except that the thickness of the transparent conductive layer was changed to 1.7 탆.

Example 3

A silver nanowire-containing solution was prepared in the same manner as in Example 1.

33 parts by weight of a solution containing a hollow silica and a fluorine-containing monomer (Pelnox, A-2505, hollow silica, including fluorine-containing monomer and initiator, refractive index: 1.33), a novolak resin-containing solution (Showa Denko, RY-25 ), 11 parts by weight of a crosslinking agent, 30 parts by weight of a solution containing hexamethoxymethylmelamine and 30 parts by weight of a solution containing an oxime ester initiator PBG304 (DKSH, 1- [9-ethyl-6- (2-methylbenzoyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane (available from Shinrytsu Co., Ltd.) as the adhesion promoter, KBM-303), and solvent propylene glycol monomethyl ether acetate was added to prepare a composition for a matrix having a solid content concentration of 1.6 wt%. The composition for a matrix contained hollow silica in an amount of 33% by weight of a fluorine-containing monomer, 46% by weight of a novolak resin, 3% by weight of hexamethoxymethylmelamine, 8% by weight of an oxime ester initiator, 2- (3,4- Hexyl) ethyltrimethoxysilane in an amount of 10% by weight.

Using the prepared silver nanowire-containing solution and the composition for a matrix, a transparent conductor having a transparent conductive layer with a thickness of 1.1 탆 was prepared in the same manner as in Example 1.

Comparative Example  One

A silver nanowire-containing solution was prepared in the same manner as in Example 1.

37 parts by weight of dipentaerythritol hexaacrylate (DPHA, Entis), 13 parts by weight of a novolak resin-containing solution (Showa Denko, RY-25) as a photosensitive resin, 34 parts by weight of a hexamethoxymethylmelamine- , A solution containing an oxime ester initiator PBG304 (DKSH, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone- O-acetyloxime)), and the solvent propylene glycol monomethyl ether acetate was added to prepare a composition for a matrix having a solid concentration of 1.6 wt%. The composition for a matrix contained 37% by weight of dipentaerythritol hexaacrylate, 52% by weight of novolak resin, 3% by weight of hexamethoxymethylmelamine and 8% by weight of oxime ester initiator based on the solids content.

Using the prepared silver nanowire-containing solution and the composition for a matrix, a transparent conductor having a transparent conductive layer with a thickness of 1.2 mu m was prepared in the same manner as in Example 1. [

Comparative Example 2

A silver nanowire-containing solution was prepared in the same manner as in Example 1.

, 30 parts by weight of a novolac resin-containing solution (Showa Denko Co., Ltd., RY-25) as a photosensitive resin, 47 parts by weight of a hexamethoxymethylmelamine-containing solution as a crosslinking agent, 100 parts by weight of a solution containing an oxime ester initiator PBG304 (DKSH, 23 parts by weight of 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- (O- acetyloxime), and propylene glycol monomethyl Ether acetate was added to prepare a composition for a matrix having a solid content concentration of 1.6 wt%. The composition for a matrix contained 89% by weight of a novolac resin, 3% by weight of hexamethoxymethylmelamine and 8% by weight of an oxime ester initiator based on the solid content.

Using the prepared silver nanowire-containing solution and the composition for a matrix, a transparent conductor having a transparent conductive layer with a thickness of 1.2 mu m was prepared in the same manner as in Example 1. [

The following properties of the transparent conductor of the examples and comparative examples were evaluated, and the results are shown in Table 1 below.

(1) adhesiveness Pattern Performance: Using the embodiment and the comparative example on the transparent conductor line width 30㎛ pattern mask (negative etch line width 30㎛ / non-etched portion width 30㎛) pattern is formed of 50mJ / cm ² . Of the exposed sample developer trimethyl ammonium hydroxide (trimethylammonium hydroxide) 5% into the aqueous developer for 30 seconds, the first washing, and after this baking for 3 minutes in 120 ℃ oven to UV exposure at 200mJ / cm ² pattern Layer. The transparent conductor on which the pattern layer was formed was immersed in an etching solution (Al etchant, 75 wt% to 85 wt% aqueous solution of phosphoric acid at 85 wt% concentration, 3 wt% to 10 wt%, 99.7 wt% (Transgenic aluminum etchant type A) of 5% by weight to 20% by weight of an aqueous acetic acid solution having a concentration of 5% by weight. The line width of the etched portion of the second cleaned transparent conductor was observed with an optical microscope (MX-50, Olympus), and the standard deviation of the line width of the etched portion formed was determined. A standard deviation of 10% or less and a good pattern formation shape is good, a standard deviation of 20% or more and a standard deviation of 20% or less and a pattern formation shape is good, a standard deviation is 20% When the pattern was not formed at all, it was evaluated as x. When the transparent conductive layer was not peeled off from the substrate layer after the first cleaning,?, When the transparent conductive layer was partially peeled, and when the transparent conductive layer was completely peeled, x.

(2) Haze and total light transmittance: Haze and total light transmittance were measured using a haze meter (NDH-2000, NIPPON DENSHOKU) at a wavelength of 400 nm to 700 nm with the conductive layer directed to the light source for the transparent conductor of Examples and Comparative Examples .

(3) Surface resistance: The sheet resistances of the transparent conductors of Examples and Comparative Examples were measured using a non-contact type sheet resistance measuring device (EC-80P, NAPSON). The sheet resistance was measured for a transparent conductive layer that was not patterned.

Hollow silica and fluorine-containing monomer-containing solution Photosensitive resin DPHA Adhesion promoter Transparent conductive layer thickness
(탆) Pattern forming property Attachment Hayes
(%) Total light transmittance
(%) Sheet resistance
(Ω / □) Example 1 include include Without Without 1.2 ◎  ○ 1.37 91.23 25.90 Example 2 include include Without Without 1.7 ◎ ○ 1.33 91.16 25.69 Example 3 include include Without include 1.1 ◎ ○ 1.39 91.19 26.26 Comparative Example 1 Without include include Without 1.2 △ △ 1.60 89.21 24.90 Comparative Example 2 Without include Without Without 1.2 △ X 1.59 88.92 25.50

As shown in Table 1, the transparent conductor according to the present embodiment can be patterned without a photoresist, so that productivity is excellent, the pattern forming ability is excellent, and the adhesion to the base layer is excellent, And was not peeled off from the substrate layer. Further, the transparent conductor according to the present example had excellent optical characteristics and low sheet resistance, thus being excellent in conductivity.

However, the comparative example not containing the hollow silica particles and the fluorine-containing monomer had poor pattern formability, and the transparent conductive layer was peeled off from the base layer after patterning, so that the adhesion was not good.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

And a transparent conductive layer formed on the substrate layer,
Wherein the transparent conductive layer comprises a metal nanowire and a matrix impregnated with the metal nanowire,
Wherein the matrix is formed from a composition for a matrix comprising inorganic hollow particles, a fluorine-containing monomer or oligomer thereof, a photosensitive resin, a crosslinking agent and an initiator.
The transparent conductor according to claim 1, wherein the transparent conductive layer has a thickness of 1 占 퐉 or more and 2 占 퐉 or less.
2. The transparent conductor of claim 1, wherein the metal nanowires are fully impregnated in the matrix.
2. The transparent conductor of claim 1, wherein the metal nanowire comprises silver nanowires.
The transparent conductor according to claim 1, wherein the inorganic hollow particles and the fluorine-containing monomer or a whole oligomer thereof or the solution containing the inorganic hollow particles and the fluorine-containing monomer or oligomer thereof as a whole have a refractive index of 1.42 or less.
The photosensitive resin composition according to claim 1, wherein the photosensitive resin is selected from the group consisting of novolac resins, aromatic hydrocarbon formaldehyde resin modified phenol resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, trimethylol methane resins, A resin, a biphenyl-modified phenol resin, a biphenyl-modified naphthol resin, and an aminotriazine-modified phenol resin.
The transparent conductor according to claim 1, wherein the composition for matrix further comprises at least one of an adhesion promoter and an antioxidant.
The composition according to claim 7, wherein the matrix composition comprises 20 to 40% by weight of the inorganic hollow particles and the fluorine-containing monomer or oligomer thereof, 40 to 60% by weight of the photosensitive resin, % To 5% by weight of said initiator, 1% to 10% by weight of said initiator, and 5% to 15% by weight of said adhesion promoter.
The transparent conductor according to claim 1, wherein the transparent conductor has a total light transmittance of 90% or more at a wavelength of 400 nm to 700 nm.
The transparent conductor according to claim 1, wherein the base layer further comprises a functional layer.
A display device comprising the transparent conductor according to any one of claims 1 to 10.

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